WO2022045344A1 - Emulsion composition and method for producing same - Google Patents

Abstract

The preset invention provides: an emulsion composition which is able to be produced by an easy method in comparison to conventional ones, while exhibiting excellent stability of an emulsion; and a method for producing this emulsion composition.　An emulsion composition which contains: a conjugated diene rubber in a liquid state; a diluent that has a vapor pressure of 10 Pa or less at 20°C; a surfactant; and water.

Description

Emulsion composition and its production method

The present invention relates to an emulsion composition having excellent emulsion stability and a method for producing the same.

Liquid rubber is widely used as an adhesive, an adhesive, a cold resistance improving agent for rubbers, a processing oil agent, a reactive plasticizer, and the like. When liquid rubber is used for these purposes, it is generally used as it is, but it may be used after being emulsified. Since the viscosity is low when the molecular weight of the liquid rubber is about several thousand, it can be easily emulsified by using a general emulsifier, but when the molecular weight of the liquid rubber is about tens of thousands, the viscosity is high. Therefore, it becomes difficult to emulsify. In this case, it is possible to emulsify by applying an extremely large mechanical shearing force, but there is a problem that dedicated equipment is required and the manufacturing process becomes complicated. Further, even if it can be emulsified, it has poor stability, so that there is a problem that phase separation occurs during storage.

As a method for solving such a problem, Patent Document 1 describes in a method of mixing an organic solvent solution (A) of a polymer and an aqueous medium (B) in the presence of an emulsifier to form an oil-in-water emulsion. A method in which the above (A) and (B) are mixed at a specific volume ratio by low-speed stirring to form a water-in-oil emulsion, and further phase-inverted by high-speed stirring to obtain an oil-in-water emulsion. Proposed. Further, in Patent Document 2, when emulsifying a liquid cis-1,4-polyisoprene rubber having a molecular weight of 10,000 to 60,000, the cis-1,4-polyisoprene rubber is dissolved in an organic solvent. There has been proposed an emulsification method characterized by using water in a range of 80 parts by mass or less at most with respect to 100 parts by mass of the liquid cis-1,4-polyisoprene rubber.
Further, Patent Document 3 proposes an emulsification method using dialkylsulfosuccinate as an emulsifier for liquid polyisoprene having a molecular weight of 10,000 to 60,000, and Patent Document 4 has a molecular weight of 10,000 to 60,000. A method for producing an emulsion using polyoxyethylene alkyl (allyl) ether phosphate as an emulsifier when emulsifying a liquid polyisoprene of 10,000 to 60,000 has been proposed.
Further, Non-Patent Document 1 describes, as a method for emulsifying liquid rubber, a method of diluting with an organic solvent, mixing with an emulsifier and water, and then distilling off the organic solvent to emulsify.

Special Publication No. 49-332 Japanese Unexamined Patent Publication No. 54-124043 Japanese Unexamined Patent Publication No. 62-141033 Japanese Unexamined Patent Publication No. 54-124040

Although the emulsion composition could be obtained by the conventional method, the stability of the emulsion was not sufficient. Further, in particular, the method of Patent Document 1 requires special equipment because it is necessary to stir the composition having a high viscosity at high speed, and it cannot be easily produced. Further, in Non-Patent Document 1, since an organic solvent is used, a step of distilling off the solvent is required, and the manufacturing method is complicated.

The subject of the present invention has been made in view of the above problems, and provides an emulsion composition which can be easily produced as compared with a conventional method and has excellent emulsion stability, and a method for producing the same. It is to be.

As a result of various studies on emulsification of liquid conjugated diene rubber, the present inventors have found a very stable emulsion composition in which phase separation is unlikely to occur when a diluent having a vapor pressure of 10 Pa or less at 20 ° C. is used. We have found that the emulsion composition can be obtained by a simpler method as compared with the conventional method, and completed the present invention.

That is, the present invention provides the following [1] to [7].
[1] An emulsion composition containing a liquid conjugated diene-based rubber, a diluent having a vapor pressure of 10 Pa or less at 20 ° C., a surfactant, and water.
[2] The emulsion composition according to the above [1], wherein the liquid conjugated diene rubber contains a monomer unit derived from one or more selected from butadiene, isoprene, and β-farnesene.
[3] The emulsion composition according to the above [1] or [2], wherein the liquid conjugated diene rubber is a modified conjugated diene rubber having a hydrogen-bonding functional group as a part of the conjugated diene rubber.
[4] The hydrogen-binding functional group is a hydroxy group, an epoxy group, an aldehyde group, an acetalized form of an aldehyde group, a carboxy group, a salt of a carboxy group, an esterified form of a carboxy group, an acid anhydride of a carboxy group, or a boronyl. The emulsion composition according to the above [3], which is one or more selected from a group, a salt of a boronyl group, an esterified product of a boronyl group, a silanol group, and an esterified product of a silanol group.
[5] The emulsion composition according to any one of [1] to [4] above, wherein the surfactant is a nonionic surfactant.
[6] The content of the surfactant in the emulsion composition is 1 to 15 parts by mass with respect to 100 parts by mass in total of the liquid conjugated diene rubber and the diluent. The emulsion composition according to any one of [5].
[7] The method for producing an emulsion composition according to any one of [1] to [6], wherein the liquid conjugated diene rubber, the diluent, the surfactant, and water are mixed. A method for producing an emulsion composition, which comprises producing an oil droplet emulsion in water and then not removing the diluent.

According to the present invention, it is possible to provide an emulsion composition which can be easily produced as compared with a conventional method and has excellent emulsion stability, and a method for producing the same.

[Emulsion composition]
The emulsion composition of the present invention is an emulsion composition containing a liquid conjugated diene rubber, a diluent having a vapor pressure of 10 Pa or less at 20 ° C., a surfactant, and water.
According to the present invention, since a liquid conjugated diene rubber and a diluent having a vapor pressure of 10 Pa or less at 20 ° C. are used in combination, it is possible to obtain an emulsion composition having excellent stability in which phase separation is unlikely to occur. It is possible. If the vapor pressure of the diluent at 20 ° C. exceeds 10 Pa, the diluent may evaporate during storage and the emulsion particles may collapse. On the other hand, when the vapor pressure of the diluent at 20 ° C. is 10 Pa or less, it is possible to suppress the disintegration of the emulsion particles. In addition, the emulsion composition of the present invention is easy to manufacture because its viscosity does not easily increase during its manufacture, and it is also excellent in handleability. Further, the contamination of the manufacturing equipment can be suppressed, and at the same time, the manufacturing method of diluting with an organic solvent can eliminate the need for the step of removing the diluent, so that the manufacturing efficiency is excellent.
Since the emulsion composition of the present invention has a stable emulsion, it can be more uniformly and efficiently adhered to the object to be adhered when it is used as an adhesive, and as a result, the adhesive strength is also improved. ..

Hereinafter, the present invention will be described in detail.
<Liquid conjugated diene rubber>
The liquid conjugated diene-based rubber used in the present invention contains at least a monomer unit derived from the conjugated diene (hereinafter, also referred to as “conjugated diene unit”) in the molecule, and for example, all of the conjugated diene-based rubbers. It is preferable that the monomer unit contains 50 mol% or more of the monomer unit derived from the conjugated diene.
In the present specification, the liquid conjugated diene rubber has a melt viscosity of 30 Pa · s or more and 4,000 Pa · s or less measured at 38 ° C. The melt viscosity is preferably 35 Pa · s or more, and more preferably 40 Pa · s or more, from the viewpoint of improving the adhesiveness. Further, from the viewpoint of improving the stability of the emulsion and improving the handleability, the melt viscosity is preferably 2,500 Pa · s or less, more preferably 1,500 Pa · s or less, 1. It is more preferably 000 Pa · s or less, and even more preferably 500 Pa · s or less. When the melt viscosity is within the above range, the dispersibility of the emulsion composition is improved and the increase in viscosity is suppressed, so that the handleability can be improved.
The melt viscosity of the liquid conjugated diene rubber means the viscosity measured at 38 ° C. using a Brookfield type viscometer (B type viscometer).

Examples of the conjugated diene monomer include butadiene, 2-methyl-1,3-butadiene (hereinafter, also referred to as “isoprene”), 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, and 2, -Methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadien, 1,3-cyclohexadiene, 2-methyl-1,3-octadien, 1,3,7-octatriene, β-farnesene (Hereinafter also referred to as "farnesen"), myrsen, chloroprene and the like can be mentioned. These conjugated diene may be used alone or in combination of two or more.
The liquid conjugated diene rubber is more preferably containing a monomer unit derived from one or more selected from butadiene, isoprene and farnesene from the viewpoint of adhesiveness when the emulsion composition is used as an adhesive.

The liquid conjugated diene rubber used in the present invention may contain a unit derived from a monomer other than the conjugated diene monomer as long as the effect of the present invention is not impaired. Examples of other monomers include copolymerizable ethylenically unsaturated monomers and aromatic vinyl compounds.
Examples of the ethylenically unsaturated monomer include olefins such as ethylene, 1-butene, and isobutylene.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, and 4 -Dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2 -Vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene and the like can be mentioned. These may be used alone or in combination of two or more.
When the liquid conjugated diene rubber contains a monomer unit derived from a monomer other than the conjugated diene monomer, the content thereof is preferably 30 mol% or less, preferably 10 mol% or less. It is more preferably present, and further preferably 5 mol% or less.

The liquid conjugated diene-based rubber used in the present invention is preferably a modified conjugated diene-based rubber having a hydrogen-binding functional group in a part of the conjugated diene-based rubber, and a conjugated diene unit is added to at least a part of the polymer chain. A modified conjugated diene-based rubber containing a hydrogen-binding functional group at the side chain or the end of the polymer chain is more preferable.
When the conjugated diene rubber is the modified conjugated diene rubber, when the emulsion composition of the present invention is used as an adhesive, the modified conjugated diene rubber interacts with the adherend to improve the adhesive force. Can be made to.

In addition, in this specification, "hydrogen bond" means a hydrogen atom (donor) which is bonded to an atom (O, N, S, etc.) having a large electronegativity and is electrically positively polarized, and a lone electron pair. It means a bond-like interaction formed with an electrically negative atom (acceptor).

In the present invention, the "hydrogen-bonding functional group" is a functional group capable of functioning as a donor and an acceptor in the hydrogen bond. Specifically, hydroxy group, epoxy group, ether group, mercapto group, carboxy group, carbonyl group, aldehyde group, amino group, imino group, imidazole group, urethane group, amide group, urea group, isocyanate group, nitrile group, Examples thereof include a boronyl group, a silanol group and derivatives thereof. Examples of the derivative of the aldehyde group include its acetalized form. Examples of the derivative of the carboxy group include the salt thereof, the esterified product thereof, the amidated product thereof, and the acid anhydride thereof. Examples of the derivative of the boronyl group include the salt thereof and the esterified product thereof. Examples of the derivative of the silanol group include its esterified product. Examples of the carboxy group include a group derived from a monocarboxylic acid and a group derived from a dicarboxylic acid.
Among these, from the viewpoint of improving the adhesiveness and the ease of producing a liquid conjugated diene rubber, hydroxy group, epoxy group, aldehyde group, esterified body of aldehyde group, carboxy group, salt of carboxy group, carboxy One or more selected from an esterified product of a group, an acid anhydride of a carboxy group, a boronyl group, a salt of a boronyl group, an esterified product of a boronyl group, a silanol group, and an esterified product of a silanol group is preferable. More preferably, one or more selected from an epoxy group, a carboxy group, a salt of a carboxy group, an esterified product of a carboxy group, an acid anhydride of a carboxy group, a boronyl group, a salt of a boronyl group, and an esterified product of a boronyl group. More preferably, one or more selected from a carboxy group, an esterified product of a carboxy group, a boronyl group, and an esterified product of a boronyl group.

The number of hydrogen-bonding functional groups in the modified conjugated diene-based rubber is preferably 0.5 or more on average per molecule from the viewpoint of improving the adhesiveness when the emulsion composition is used as an adhesive. Two or more are more preferable, and three or more are further preferable. The number of hydrogen-bonding functional groups is preferably 80 or less per molecule, preferably 40 or less, from the viewpoint of controlling the viscosity of the modified conjugated diene rubber in an appropriate range and improving the handleability. The number is more preferably less than, more preferably 20 or less, and even more preferably 10 or less.

The average number of hydrogen-bonding functional groups per molecule of modified conjugated diene-based rubber is calculated from the equivalent of hydrogen-bonding functional groups (g / eq) of the modified conjugated diene-based rubber and the number average molecular weight Mn in terms of styrene based on the following formula. Will be done. The equivalent of the hydrogen-bonding functional group of the modified conjugated diene-based rubber means the mass of the conjugated diene bonded to one hydrogen-bonding functional group and other monomers other than the conjugated diene contained as necessary. do.
Average number of hydrogen-bonding functional groups per molecule = [(number average molecular weight (Mn)) / (molecular weight of styrene unit) × (conjugated diene and, if necessary, average of other monomer units other than conjugated diene) Molecular weight)] / (equivalent to hydrogen-bonding functional group)
The method for calculating the equivalent of the hydrogen-bonding functional group can be appropriately selected depending on the type of the hydrogen-bonding functional group.

Examples of the method for obtaining the modified conjugated diene-based rubber include a method obtained by adding a modified compound to a polymerized product of the conjugated diene monomer (hereinafter, also referred to as “production method (1)”), and a conjugated diene polymer. (Hereinafter, also referred to as "manufacturing method (2)"), a method obtained by copolymerizing a conjugated diene monomer and a radically polymerizable compound having a hydrogen-binding functional group (hereinafter, also referred to as "manufacturing method (2)"). Also referred to as "production method (3)"), a modified compound capable of reacting with the polymerization active terminal is added to the polymer of the unmodified conjugated diene monomer having a polymerization active end before the polymerization terminator is added. (Hereinafter, also referred to as “manufacturing method (4)”).

[Manufacturing method of modified conjugated diene rubber (1)]
The production method (1) is a method of adding a modified compound to a polymerized conjugated diene monomer, that is, an unmodified conjugated diene-based rubber (hereinafter, also referred to as “unmodified conjugated diene-based rubber”).
The unmodified conjugated diene-based rubber can be obtained by polymerizing a conjugated diene and, if necessary, a monomer other than the conjugated diene by, for example, an emulsion polymerization method, a solution polymerization method, or the like.

As the solution polymerization method, a known or known method can be applied. For example, a monomer containing a predetermined amount of conjugated diene in a solvent using a Cheegler catalyst, a metallocene catalyst, an anionic polymerizable active metal or active metal compound, optionally in the presence of a polar compound. To polymerize.
Examples of the solvent include aliphatic hydrocarbons such as n-butane, n-pentane, isopentan, n-hexane, n-heptane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; benzene, Examples thereof include aromatic hydrocarbons such as toluene and xylene.

Examples of the anion-polymerizable active metal include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium; and lanthanoid-based rare earth metals such as lanthanum and neodym. .. Among these anionic polymerizable active metals, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
As the anionic polymerizable active metal compound, an organic alkali metal compound is preferable. Examples of the organic alkali metal compound include organic monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; , 1,4-Dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and other polyfunctional organic lithium compounds; sodium naphthalene, potassium naphthalene and the like. Among these organic alkali metal compounds, an organic lithium compound is preferable, and an organic monolithium compound is more preferable.

The amount of the organic alkali metal compound used can be appropriately set according to the melt viscosity, molecular weight, etc. of the target unmodified conjugated diene rubber and modified conjugated diene rubber, but 100 parts by mass of all the monomers containing the conjugated diene. However, it is usually used in an amount of 0.01 to 3 parts by mass.
The organic alkali metal compound can also be used as an organic alkali metal amide by reacting with a secondary amine such as dibutylamine, dihexylamine, or dibenzylamine.

Polar compounds are usually used in anionic polymerization to condition the microstructure of the conjugated diene moiety without inactivating the reaction. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and ethylene glycol diethyl ether, 2,2-di (2-tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides and phosphines. Examples include compounds. The polar compound is usually used in an amount of 0.01 to 1,000 mol with respect to the organic alkali metal compound.
The temperature of the solution polymerization is usually in the range of −80 to 150 ° C., preferably in the range of 0 to 100 ° C., and more preferably in the range of 10 to 90 ° C. The polymerization mode may be either a batch type or a continuous type.
The polymerization reaction can be stopped by adding a polymerization inhibitor. Examples of the polymerization terminator include alcohols such as methanol and isopropanol. The unmodified conjugated diene-based rubber can be isolated by pouring the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate a polymerized product, or by washing the polymerization reaction solution with water, separating and drying.
Among the above methods, the solution polymerization method is preferable as the method for producing the unmodified conjugated diene-based rubber.

As the emulsification polymerization method, a known or known method can be applied. For example, a monomer containing a predetermined amount of conjugated diene is emulsified and dispersed in the presence of an emulsifier, and emulsion polymerization is carried out by a radical polymerization initiator.
Examples of the emulsifier include long-chain fatty acid salts having 10 or more carbon atoms and rosin salts. Examples of the long-chain fatty acid salt include potassium salts and sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid.
Water is usually used as the dispersion solvent, and a water-soluble organic solvent such as methanol or ethanol may be contained as long as the stability during polymerization is not impaired.
Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
A chain transfer agent may be used to adjust the molecular weight of the resulting unmodified conjugated diene rubber. Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, turpinolene, γ-terpinene, α-methylstyrene dimer and the like.

The temperature of emulsion polymerization can be appropriately set depending on the type of radical polymerization initiator used, etc., but is usually in the range of 0 to 100 ° C, preferably in the range of 0 to 60 ° C. The polymerization mode may be either continuous polymerization or batch polymerization.

The polymerization reaction can be stopped by adding a polymerization inhibitor. Examples of the polymerization terminator include amine compounds such as isopropylhydroxylamine, diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.

After the polymerization reaction is stopped, an antiaging agent may be added if necessary. After the polymerization reaction is stopped, unreacted monomers are removed from the obtained latex as needed, and then salts such as sodium chloride, calcium chloride and potassium chloride are used as coagulants, and if necessary, nitrates, sulfuric acid and the like are used. The polymer is recovered by coagulating the polymer while adjusting the pH of the coagulation system to a predetermined value by adding an acid, and then separating the dispersion solvent. Then, by washing with water, dehydrating, and then drying, an unmodified conjugated diene-based rubber can be obtained. At the time of solidification, if necessary, latex and extended oil prepared as an emulsified dispersion may be mixed and recovered as an oil-expanded unmodified conjugated diene-based rubber.

(Modified compound used in manufacturing method (1))
The modified compound used in the production method (1) is not particularly limited, but one having a hydrogen-bonding functional group is preferable from the viewpoint of improving the adhesiveness when the emulsion composition is used as an adhesive. Examples of the hydrogen-bonding functional group include the same as described above. Among them, from the viewpoint of the strength of hydrogen bonding force, hydroxy group, epoxy group, aldehyde group, acetalized form of aldehyde group, carboxy group, salt of carboxy group, esterified form of carboxy group, acid anhydride of carboxy group. Preferables are a product, a boronyl group, a salt of a boronyl group, an esterified form of a boronyl group, a silanol group, and an esterified form of a silanol group.

Examples of the modified compound include unsaturated carboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid; unsaturated such as maleic anhydride, citraconic acid anhydride, 2,3-dimethylmaleic acid anhydride, and itaconic acid anhydride. Carboxylic acid anhydride; unsaturated carboxylic acid ester such as maleic acid ester, fumaric acid ester, citraconic acid ester, itaconic acid ester; unsaturated carboxylic acid amide such as maleic acid amide, fumaric acid amide, citraconic acid amide, itaconic acid amide. Saturated carboxylic acid imides such as maleic acid imide, fumaric acid imide, citraconic acid imide, itacone acid imide; vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyltriethoxysilane , 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 2-Mercaptoethylmethoxydimethylsilane, 2-Mercaptoethylethoxydimethylsilane, 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3 -Mercaptpropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxyethylsilane, 3-mercaptopropyldiethoxyethylsilane, 3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropylethoxydimethylsilane, etc. Silane compounds; examples thereof include boronates such as triethyl borate, tripropyl borate, triisopropyl borate and tributyl borate. One of these modified compounds having a hydrogen-bonding functional group may be used alone, or two or more thereof may be used in combination.

The amount of the modified compound used is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and further preferably 1 to 30 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene rubber. Is.
The reaction temperature is usually preferably in the range of 0 to 200 ° C, more preferably in the range of 50 to 200 ° C.
Further, after the modified compound is grafted onto an unmodified conjugated diene rubber to introduce a hydrogen-bonding functional group, a modified compound capable of reacting with the functional group is further added to another hydrogen-bonding functional group in the polymer. May be introduced in. Specifically, for example, a compound having a hydroxyl group such as 2-hydroxyethyl methacrylate or methanol after grafting maleic anhydride on an unmodified conjugated diene rubber obtained by living anionic polymerization, a compound such as water, etc. There is a method of reacting.

The amount of the modified compound added to the modified conjugated diene rubber is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene rubber. , 1.5 to 20 parts by mass is more preferable. The amount of the modified compound added to the modified conjugated diene rubber can be calculated based on the acid value of the modified compound, and various analytical instruments such as infrared spectroscopy and nuclear magnetic resonance spectroscopy are used. You can also ask for it.

The method for adding the modified compound to the unmodified conjugated diene rubber is not particularly limited, and for example, a liquid unmodified conjugated diene rubber, an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative, a boronic acid derivative, and a silane compound are used. Examples thereof include a method of adding one or more modified compounds selected from the above and, if necessary, a radical generator, and heating in the presence or absence of an organic solvent. The radical generator to be used is not particularly limited, and commercially available organic peroxides, azo compounds, hydrogen peroxide and the like can be used.
Examples of the organic solvent used in the above method generally include a hydrocarbon solvent and a halogenated hydrocarbon solvent. Among these organic solvents, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene and xylene are preferable.

Further, when the reaction for adding the modified compound is carried out by the above method, an antiaging agent may be added from the viewpoint of suppressing side reactions. As the antioxidant, commercially available products can be used, for example, butylated hydroxytoluene (BHT), N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (Nocrack 6C) and the like. Can be mentioned.

The amount of the antiaging agent added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the unmodified conjugated diene rubber. When the amount of the antiaging agent added is within the above range, side reactions can be suppressed and a modified conjugated diene rubber can be obtained in good yield.

[Manufacturing method of modified conjugated diene rubber (2)]
Examples of the production method (2) include a method of obtaining an oxidation-conjugated diene-based rubber having a functional group or a bond containing oxygen generated by an oxidation reaction in the molecule by oxidizing the conjugated diene-based rubber as a raw material. Specific examples of the functional group and the bond include a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, an ether bond and the like.
As a method for oxidizing the raw material conjugated diene rubber, a method of heat treatment at a temperature higher than the oxidation temperature (hereinafter, also referred to as "manufacturing method (2-1)") and irradiation with light having an absorption wavelength of the raw material conjugated diene rubber are used. Examples thereof include a method of activating with and reacting with oxygen (hereinafter, also referred to as “production method (2-2)”). Above all, a method (manufacturing method (2-1)) obtained by heat-treating the raw material conjugated diene-based rubber at a temperature equal to or higher than the oxidation temperature is preferable.

[Method for Producing Oxidized Conjugated Diene Rubber (2-1)]
The manufacturing method (2-1) is a method of heat-treating a raw material conjugated diene-based rubber at a temperature equal to or higher than the oxidation temperature. The heat treatment is performed in an atmosphere containing oxygen, preferably in an air atmosphere.
The temperature of the heat treatment is not particularly limited as long as it oxidizes the raw material conjugated diene rubber, but is preferably 150 ° C. or higher, preferably 170 ° C. or higher, from the viewpoint of increasing the reaction rate of oxidation and improving productivity. It is more preferable that the temperature is 190 ° C. or higher.
The heat treatment time is not particularly limited as long as the raw material conjugated diene rubber does not deteriorate, but is preferably 30 minutes or less, and more preferably 20 minutes or less.
Further, the temperature required for the oxidation reaction can be lowered by adding a thermal radical generator to the raw material conjugated diene-based rubber.

Examples of the thermal radical generator include peroxides, azo compounds, redox-based initiators and the like. Of these, peroxides are preferable from the viewpoint that the thermal radical generator binds to the conjugated diene rubber and a structure containing oxygen is added to the conjugated diene rubber.
Examples of the peroxide include t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctanoate, t-butyl peroxyneodecanoate, and t-butyl peroxyisobutyrate. -Butyl, lauroyl peroxide, t-amyl peroxypivalate, t-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate and the like can be mentioned.

Examples of the azo compound include azobisisobutyronitrile (AIBN), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), and 4,4'-azobis. (4-Pentanoic acid), 1,1'-azobis (cyclohexanecarbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -Bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl) propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidin ) Dichloride, 2,2'-azobis (N, N-dimethyleneisobutyryamide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propion Amid), 2,2'-azobis (isobutyry amide) dihydrate and the like. The thermal radical generator may be used alone or in combination of two or more.

Further, a redox-based initiator may be used as the thermal radical generator. Examples of the redox-based initiator include a combination of supersulfate, acidic sodium bisulfite and ferrous sulfate, t-butylhydroperoxide, a combination of acidic sodium bisulfite and ferrous sulfate, and p-. Examples thereof include a combination of mentan hydroperoxide, ferrous sulfate, sodium ethylenediamine tetraacetate, and sodium formaldehyde sulfoxylate.

[Manufacturing method of oxidation-conjugated diene-based rubber (2-2)]
The production method (2-2) is a method of activating the raw material conjugated diene-based rubber by irradiating it with light having an absorption wavelength and reacting it with oxygen.
The production method (2-2) is carried out in an atmosphere containing oxygen, preferably in an air atmosphere. The wavelength of the light used is not particularly limited as long as it is a wavelength that is absorbed by the raw material conjugated diene rubber and causes a radical reaction, but ultraviolet rays that are strongly absorbed by the raw material conjugated diene rubber are preferable.
Further, by adding a photoradical generator to the raw material conjugated diene-based rubber, it is possible to reduce the irradiation amount of light required for the oxidation reaction.

Examples of the photoradical generator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene and anthraquinone. Triphenylamine, carbazole, 3-methylacetophenone, 4,4'-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 2 -Hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide , Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. The photoradical generator may be used alone or in combination of two or more.

[Method for manufacturing modified conjugated diene rubber (3)]
Examples of the production method (3) include a method of random copolymerization, block copolymerization or graft copolymerization of a conjugated diene monomer and a radically polymerizable compound having a hydrogen-bonding functional group by a known method.

(Radical polymerizable compound having a hydrogen-bonding functional group used in the production method (3))
The radically polymerizable compound having a hydrogen-bonding functional group used in the production method (3) is not particularly limited as long as it is a compound having both a hydrogen-bonding functional group and a reactive multiple bond in the molecule. Specifically, an aldehyde having a reactive multiple bond, an acetalized form of the aldehyde; a monocarboxylic acid having a reactive multiple bond, a salt of the monocarboxylic acid, an esterified product of the monocarboxylic acid, the mono. Acid anhydride of carboxylic acid; dicarboxylic acid having reactive multiple bonds, salt of the dicarboxylic acid, esterified product of the dicarboxylic acid, acid anhydride of the dicarboxylic acid; and amine compound having reactive multiple bonds, etc. Can be mentioned.

Among the aldehydes having a multiple bond, examples of the aldehyde having a reactive carbon-carbon double bond include achlorine, metachlorine, crotonaldehyde, 3-butenal, 2-methyl-2-butenal, and 2-methyl-3. -Butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3-pentenal, 3-methyl-4 -Pentenal, 4-Pentenal, 4-Methyl-4-Pentenal, 2-Hexenal, 3-Hexenal, 4-Hexenal, 5-Hexenal, 7-Octenal, 10-Undecenal, 2-Ethylcrotonaldehyde, 3- (dimethylamino) ) Alkenals with 3 to 30 carbon atoms such as achlorein, myristolene aldehyde, palmitre aldehyde, olein aldehyde, eridine aldehyde, baxen aldehyde, gadrain aldehyde, elca aldehyde, nervone aldehyde, linole aldehyde, citroneral, cinnam aldehyde, and vanillin, preferably. Is an alkenyl with 3 to 25 carbon atoms; an aldehyde with 5 to 30 carbon atoms such as 2,4-pentadienal, 2,4-hexadienal, 2,6-nonazienal, and citral, preferably 5 carbon atoms. Alkadienal of ~ 25; alkatorienal having 7 to 30 carbon atoms such as linolenealdehyde and eleostearaldehyde, preferably alkathrienal having 7 to 25 carbon atoms; Alkatetraenal having 30 carbon atoms, preferably alkatetraenal having 9 to 25 carbon atoms; alkapentaenal having 11 to 30 carbon atoms such as eikosapentaene aldehyde, preferably alkapentaenal having 11 to 25 carbon atoms; etc. Examples thereof include unsaturated aldehydes. The aldehydes in which the cis-trans isomer is present include both cis and trans isomers. These aldehydes may be used alone or in combination of two or more.

Among the acetalized forms of the aldehyde having the multiple bonds, the acetalized form of the aldehyde having the reactive carbon-carbon double bond is the acetalized form of the aldehyde, specifically 2-methyl-3-butenal. 3- (1,3-dioxalan-2-yl) -3-methyl-1-propene, which is an acetalized form, and 3- (1,3-dioxalan-2), which is an acetalized form of 3-methyl-3-butenal. -Il) -2-methyl-1-propen and the like can be mentioned.

Among the aldehyde having a multiple bond and the acetalized form of the aldehyde, the aldehyde having a reactive carbon-carbon triple bond and the acetalized form thereof include propiolaldehyde, 2-butin-1-ar, and 2-pentyne. Examples thereof include aldehydes having a carbon-carbon triple bond such as -1-ar, and acetalized forms of the aldehydes.

Among the aldehyde having a multiple bond and the acetalized form of the aldehyde, an aldehyde having a reactive carbon-carbon double bond is preferable, and for example, acrolein, metachlorine, crotonaldehyde, 3-butenyl, 2-methyl-2- Butenal, 2-methyl-3-butenal, 2,2-dimethyl-3-butenal, 3-methyl-2-butenal, 3-methyl-3-butenal, 2-pentenal, 2-methyl-2-pentenal, 3- Pentenal, 3-methyl-4-pentenal, 4-pentenal, 4-methyl-4-pentenal, 2-hexenal, 3-hexenal, 4-hexenal, 5-hexenal, 7-octenal, 2-ethylcrotonaldehyde, 3- One or more selected from (dimethylamino) acrolein and 2,4-pentadienal is preferable. Among them, one or more selected from acrolein, methacrolein, crotonaldehyde, and 3-butenal are more preferable because of their good reactivity at the time of copolymerization.

Examples of the monocarboxylic acid having a multiple bond, the salt of the monocarboxylic acid, the esterified product of the monocarboxylic acid, and the acid anhydride of the monocarboxylic acid include (meth) acrylic acid and (meth) acrylic acid. Sodium salt, potassium salt of (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate , (Meta) 2-hydroxypropyl acrylate, (meth) 3-hydroxypropyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxylbutyl (meth) acrylate, 4-hydroxylbutyl (meth) acrylate , (Meta) vinyl acrylate, 2- (trifluoromethyl) acrylate, 2-trifluoromethyl acrylate methyl, 2-trifluoromethyl acrylate ethyl, 2-trifluoromethyl acrylate propyl, 2-trifluoromethyl 2-butyl acrylate, 2-hydroxylethyl 2-trifluoromethyl acrylate, vinyl 2-trifluoromethyl acrylate, methyl silicate, vinyl silicate, methyl crotonate, vinyl crotonate, 3-methyl-3 -Methyl butenoate, 3-Methyl-3-Vinite butenoate, Methyl 4-pentateate, Vinyl 4-Pentate, 2-Methyl-4-Methyl pentate, 2-Methyl-4-Vinite pentate, 5-Hexen Methyl acid, vinyl 5-hexenoate, methyl 3,3-dimethyl-4-pentate, vinyl 3,3-dimethyl-4-pentenate, methyl 7-octenoate, vinyl 7-octene, trans-3-penten Methyl acid, vinyl trans-3-pentenate, methyl trans-4-decenoate, vinyl trans-4-decenoate, ethyl 3-methyl-3-butenoate, ethyl 4-pentenate, 2-methyl-4-pentene Ethyl acid, ethyl 5-hexenoate, ethyl 3,3-dimethyl-4-pentate, ethyl 7-octenoate, ethyl trans-3-pentenate, ethyl trans-4-decenoate, methyl 10-undecenoate, 10 -Vinyl undecenoate, (meth) acrylic acid anhydride, 2- (trifluoromethyl) acrylic acid anhydride, cinnamic acid anhydride, crotonic acid anhydride, 3-methyl-3-butenoic acid anhydride, 4-pentene Acid anhydride, 2-methyl-4-pentenoic acid anhydride, 5-hexenoic acid anhydride, 3,3-dimethyl-4-pentenoic acid anhydride, 7 -Octenic acid anhydride, trans-3-pentenoic acid anhydride, trans-4-decenoic acid anhydride, 3-methyl-3-butenoic acid anhydride, 4-pentenoic acid anhydride, 2-methyl-4-pentenic acid Carboxylic acids with reactive carbon-carbon double bonds such as anhydrides and 10-undecenoic acid anhydrides, salts of the carboxylic acid, esterifieds of the carboxylic acid, and acid anhydrides of the carboxylic acid; propiole acid. , Carboxylic acid having a reactive carbon-carbon triple bond such as methyl propiolate, ethyl propiolate, vinyl propiolate, tetrol acid, methyl tetrolate, ethyl tetrolate, and vinyl tetrolate and esterifieds of the carboxylic acid. Can be mentioned.
In addition, in this specification, the said "(meth) acrylic acid" means the generic term of "acrylic acid" and "methacrylic acid".

Examples of the dicarboxylic acid having a multiple bond, the salt of the dicarboxylic acid, the esterified product of the dicarboxylic acid, and the acid anhydride of the dicarboxylic acid include maleic acid, sodium maleic acid salt, potassium maleic acid salt, and maleic acid. Reactive carbon-carbon double bonds such as methyl, dimethyl maleate, maleic anhydride, itaconic acid, methyl itaconate, dimethyl itaconate, itaconic acid anhydride, hymic acid, methyl hymicate, dimethyl hymic acid, and hymicic acid anhydride Examples thereof include a dicarboxylic acid having a dicarboxylic acid, a salt of the dicarboxylic acid, an esterified product of the dicarboxylic acid, and an acid anhydride of the dicarboxylic acid.

The monocarboxylic acid having a multiple bond, the salt of the monocarboxylic acid, the esterified product of the monocarboxylic acid, the monocarboxylic acid anhydride, the dicarboxylic acid having the multiple bond, the salt of the dicarboxylic acid, the dicarboxylic acid. As the esterified product and the acid anhydride of the dicarboxylic acid, a compound having a reactive carbon-carbon double bond is preferable, and among them, methyl (meth) acrylate is good because the reactivity at the time of copolymerization is good. , (Meta) ethyl acrylate, (meth) butyl acrylate, (meth) vinyl acrylate, (meth) acrylate anhydride, 2- (trifluoromethyl) acrylate anhydride, silicate anhydride, crotonic acid One or more selected from anhydrate, methyl maleate, dimethyl maleate, maleic anhydride, methyl itaconate, dimethyl itaconate, and itaconic acid anhydride are more preferable.

Among the amine compounds having a multiple bond, examples of the amine compound having a reactive carbon-carbon double bond include allylamine, 3-butenylamine, 4-pentenylamine, 5-hexenylamine, 6-heptenylamine, and 7-octenylamine. , Oleylamine, 2-methylallylamine, 4-aminostyrene, 4-vinylbenzylamine, 2-allylglycine, S-allylcysteine, α-allylalanine, 2-allylaniline, geranylamine, bigabatrin, 4-vinylaniline, and 4-Vinyloxyaniline and the like can be mentioned. Among these, at least one selected from allylamine, 3-butenylamine, and 4-pentenylamine is preferable because the reactivity at the time of copolymerization is good.

[Method for manufacturing modified conjugated diene rubber (4)]
In the production method (4), a polymerized product of an unmodified conjugated diene monomer having a polymerization active terminal (unmodified conjugated diene-based rubber) is reacted with the polymerization active terminal before adding a polymerization terminator. It is a method of adding a modified compound to be obtained. The unmodified conjugated diene-based rubber having a polymerization active terminal can be obtained by, for example, an emulsion polymerization method, a solution polymerization method, or the like, in the same manner as in the above-mentioned production method (1), other than the conjugated diene monomer and, if necessary, the conjugated diene. It can be obtained by polymerizing the monomer of.
Examples of the modified compound that can be used in the production method (4) include dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, and the like. Boronic acid esters such as 2,4-tolylene diisocyanate, carbon dioxide, ethylene oxide, succinic anhydride, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, boronic acid anhydride groups, phenylboronic acid Boronic acid anhydrides such as anhydrides, modifiers such as 4,4'-bis (diethylamino) benzophenone, N-vinylpyrrolidone, N-methylpyrrolidone, 4-dimethylaminobenzilidenaniline, dimethylimidazolidinone, or JP-A 2011. Other modifiers described in Japanese Publication No. 132298 may be mentioned.

The amount of the modified compound used in the production method (4) is preferably in the range of 0.01 to 100 mol equivalent with respect to the organic alkali metal compound, for example, when polymerizing using the organic alkali metal compound. The reaction temperature is usually −80 to 150 ° C., preferably 0 to 100 ° C., more preferably 10 to 90 ° C.
Further, before adding the polymerization terminator, the modified compound is added to introduce a hydrogen-bonding functional group into the unmodified conjugated diene rubber, and then another modified compound capable of reacting with the functional group is added to another hydrogen. Bonding functional groups may be introduced into the polymer.

The modified conjugated diene-based rubber contains a unit derived from a monomer other than the conjugated diene monomer and a radically polymerizable compound having a hydrogen-bonding functional group to the extent that the effect of the present invention is not impaired. You may. Examples of other monomers include copolymerizable ethylenically unsaturated monomers and aromatic vinyl compounds, and the specific compounds and contents are the same as described above.

The method for producing the modified conjugated diene rubber is not particularly limited, but from the viewpoint of productivity, it is preferably produced by the production method (1), (2) or (3), and the production method (1) or (3). It is more preferable to produce by the production method (1), and it is further preferable to produce by the production method (1).

[Physical characteristics of liquid conjugated diene rubber]
The weight average molecular weight (Mw) of the liquid conjugated diene rubber is preferably 2,000 or more, preferably 5,000 or more, from the viewpoint of improving the adhesiveness when the emulsion composition is used as an adhesive. More preferably, it is more preferably 10,000 or more, further preferably 15,000 or more, further preferably 20,000 or more, and particularly preferably 25,000 or more. .. Further, from the viewpoint of maintaining the adhesive strength for a long period of time, it is more preferably 35,000 or more. From the viewpoint of improving the handleability of the liquid conjugated diene rubber, it is preferably 150,000 or less, more preferably 120,000 or less, further preferably 100,000 or less, and 75,000. The following is even more preferable.
Mw and Mn of the liquid conjugated diene rubber are polystyrene-equivalent weight average molecular weight and number average molecular weight obtained from the measurement of gel permeation chromatography (GPC).

The molecular weight distribution (Mw / Mn) of the liquid conjugated diene rubber is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and 1.0 to 2.0. Is even more preferable, and 1.0 to 1.3 is even more preferable. When Mw / Mn is within the above range, the viscosity variation of the liquid conjugated diene rubber is small and the handling is easy. The molecular weight distribution (Mw / Mn) means the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) in terms of standard polystyrene obtained by GPC measurement.

The glass transition temperature (Tg) of a liquid conjugated diene-based rubber may vary depending on the vinyl content of the conjugated diene unit, the type of the conjugated diene, the content of a unit derived from a monomer other than the conjugated diene, and the like. It is preferably −100 to 10 ° C., more preferably −100 to −10 ° C., and even more preferably −100 to −20 ° C. When Tg is within the above range, high viscosity can be suppressed and handling becomes easy.
The glass transition temperature (Tg) of the liquid conjugated diene rubber means a value measured by differential scanning calorimetry (DSC), and can be specifically measured by the method described in Examples.

<Diluent having a vapor pressure of 10 Pa or less at 20 ° C>
In the present invention, a diluent having a vapor pressure of 10 Pa or less at 20 ° C. is used. The specific diluent is not particularly limited, and examples thereof include oil and low-viscosity liquid rubber.
In the present invention, the low-viscosity liquid rubber refers to a rubber having a melt viscosity of less than 30 Pa · s measured at 38 ° C., and is different from the liquid conjugated diene rubber in terms of melt viscosity.
Further, in the present specification, the "diluent having a vapor pressure at 20 ° C. of 10 Pa or less" may be simply referred to as a "diluent".

When the vapor pressure of the diluent at 20 ° C. exceeds 10 Pa, it becomes difficult to stabilize the emulsion. Further, when the emulsion composition of the present invention is used as an adhesive, coating spots are likely to occur, so that the adhesiveness may decrease. In addition, manufacturing equipment may be contaminated during manufacturing. From these viewpoints, the vapor pressure of the diluent at 20 ° C. is preferably 5.0 Pa or less, more preferably 1.0 Pa or less, and further preferably 1.0 × 10 ^-1 Pa or less. It is more preferably 1.0 × 10 ⁻² Pa or less, and even more preferably 1.0 × 10 ⁻³ Pa or less. Further, it is preferable that the vapor pressure of the diluent at 20 ° C. is 1.0 × ^10-8 Pa or more.
In the present invention, the vapor pressure of the diluent having a vapor pressure of less than 103 Pa at ²⁰ ° C. is an optimum curve obtained by applying the Antoine equation to the measured value measured by the gas flow method. The value calculated by.
The vapor pressure of a diluent having a vapor pressure of more than 103 Pa at ²⁰ ° C. is a value directly measured by using a static method.

〔oil〕
As the diluent, it is preferable to use, for example, non-volatile oil. The oil is not particularly limited as long as it has a vapor pressure of 10 Pa or less at 20 ° C. and is compatible with a liquid conjugated diene-based rubber, and examples thereof include natural oils and synthetic oils. Examples of natural oils include mineral oils and vegetable oils.
The mineral oil includes paraffin-based mineral oil, aromatic mineral oil, naphthen-based mineral oil, and wax (gas) produced by Fisher Tropusch process, etc., obtained by ordinary refining methods such as solvent refining and hydrogenation refining. Tulique wax), mineral oil produced by isomerizing the wax, and the like.
Examples of commercially available paraffin-based mineral oils include the "Diana Process Oil" series manufactured by Idemitsu Kosan Co., Ltd., the "Super Oil" series manufactured by JX Energy Co., Ltd., and the "SUNPAR 150" manufactured by Nippon Sun Oil Co., Ltd.
Examples of commercially available naphthenic mineral oils include "SUNTHENE 250J" manufactured by Nippon Sun Oil Co., Ltd.

Vegetable oils include, for example, flaxseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, southern ka oil, sunflower oil, red flower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil. , Peanut oil, cottonseed oil, coconut oil, palm kernel oil, rice bran oil and the like.
Examples of the synthetic oil include hydrocarbon-based synthetic oils, ester-based synthetic oils, ether-based synthetic oils, and the like. Examples of the hydrocarbon-based synthetic oil include α-olefin oligomers such as polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, and ethylene-propylene copolymer, or hydrides thereof, alkylbenzene, and alkylnaphthalene. .. Examples of the ester-based synthetic oil include triglycerin fatty acid ester, diglycerin fatty acid ester, monoglycerin fatty acid ester, monoalcohol fatty acid ester, and polyhydric alcohol fatty acid ester. Examples of the ether-based synthetic oil include polyoxyalkylene glycol and polyphenyl ether. Examples of commercially available synthetic oils include "Linearlen" series manufactured by Idemitsu Kosan Co., Ltd., "FGC32", "FGC46" and "FGC68" manufactured by ANDEROL.

The oil may be one selected from the above natural oils and synthetic oils, but two or more kinds of natural oils, two or more kinds of synthetic oils, or a mixture of one or more kinds of natural oils and synthetic oils. But it may be.

The flash point of the oil used in the present invention is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, further preferably 130 ° C. or higher, and 140 ° C. or higher from the viewpoint of safety. Is even more preferable. The upper limit of the flash point of the oil is not particularly limited, but is preferably 320 ° C. or lower.

[Low viscosity liquid rubber]
It is also preferable to use a low-viscosity liquid rubber as the diluent. The low-viscosity liquid rubber is not particularly limited as long as the melt viscosity measured at 38 ° C. is less than 30 Pa · s and the vapor pressure at 20 ° C. is 10 Pa or less. More specifically, liquid butadiene rubber, liquid isoprene rubber, liquid farnesene rubber and the like can be mentioned, and these may be homopolymers (homopolymers) or copolymers. In particular, since it is diluted, it is preferable to have a low viscosity, a low molecular weight liquid rubber is preferable, and a liquid butadiene rubber and a liquid farnesene rubber are particularly preferable.

When the low-viscosity liquid rubber is a liquid butadiene rubber, the weight average molecular weight is preferably 500 to 10,000, more preferably 700 to 7,000, and further preferably 800 to 6,000. preferable. On the other hand, when the low-viscosity liquid rubber is a liquid farnesene rubber, the weight average molecular weight is preferably 1,000 to 80,000, preferably 1,000 to 50,000, and 1,000 to 30, It is more preferably 000, and even more preferably 1,000 to 10,000.
When the weight average molecular weight of the low-viscosity liquid rubber is within the above range, the stability of the emulsion is further improved and the handleability of the emulsion composition is also improved.
The weight average molecular weight of the low-viscosity liquid rubber is a polystyrene-equivalent weight average molecular weight obtained from the measurement of gel permeation chromatography (GPC).

In the present invention, the diluent is preferably a naphthenic mineral oil or a low-viscosity liquid rubber, preferably a naphthenic mineral oil or a liquid butadiene rubber, from the viewpoint of improving the stability of the emulsion and the adhesiveness of the adhesive using the emulsion composition. Is more preferable.

<Surfactant>
The surfactant used in the present invention is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among these, a nonionic surfactant is preferable from the viewpoint of improving the stability of the emulsion. These may be used alone or in combination of two or more.

Examples of the cationic surfactant include alkylammonium acetates, alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, oxyalkylenealkylamines, polyoxyalkylenealkylamines and the like. .. These cationic surfactants may be used alone or in combination of two or more, if necessary.

Examples of the anionic surfactant include carboxylates such as fatty acid soap, higher alcohol sulfate ester salts, higher alkyl polyalkylene glycol ether sulfate ester salts, sulfate ester salts of styrated phenol alkylene oxide adducts, and alkyl phenol alkylene oxide adducts. Sulfate ester salt, sulfated oil, sulfated fatty acid ester, sulfated fatty acid, sulfated olefin and other sulfate ester salts, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate, naphthalene sulfonic acid and the like formalin condensation Examples thereof include products, α-olefin sulfonates, paraffin sulfonates, sulfonates such as sulfosulphonic acid diester salts, higher alcohol phosphate ester salts and the like. These anionic surfactants may be used alone or in combination of two or more, if necessary.
Examples of commercially available anionic surfactants include "Plysurf A210B" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and "Phosphanol RD-720N" manufactured by Toho Chemical Industry Co., Ltd.

Examples of the nonionic surfactant include a higher alcohol alkylene oxide adduct, an alkylphenol alkylene oxide adduct, a styrated phenolalkylene oxide adduct, a fatty acid alkylene oxide adduct, a polyhydric alcohol aliphatic ester alkylene oxide adduct, and a higher alkylamine. Examples thereof include polyoxyalkylene type nonionic surfactants such as alkylene oxide adducts and fatty acid amide alkylene oxide adducts, and polyhydric alcohol type nonionic surfactants such as alkyl glycoloxides and sucrose fatty acid esters. These nonionic surfactants may be used alone or in combination of two or more, if necessary.
Commercially available nonionic surfactants include "Adecator PC-6", "Adecator PC-8", "Adecator PC-10", "Adecator TN-100" manufactured by ADEKA Co., Ltd., and manufactured by Toho Chemical Industry Co., Ltd. Examples thereof include polyoxyethylene alkyl ethers (trade names “Pegnol TE-10A”, “Pegnol L-9A”, “Pegnol TH-8”) and the like.

The HLB (Hydrophilic-Lipophilic Balance) value of the nonionic surfactant is an index showing the balance between hydrophilicity and lipophilicity, and is expressed by a value from 0 to 20. In the present invention, the value calculated by the following formula (I) based on the Griffin method is used.
HLB value = 20 × total formula weight of hydrophilic part / molecular weight (I)

For identification of nonionic surfactants, the molecular weight and structural units can be detected and measured using mass spectra, the structure can be detected and measured using 1H and ¹³ C ^- NMR, and the structure can be identified based on these. It is possible to obtain the HLB value using the formula (I) based on the obtained information. Examples of the method for separating the nonionic surfactant from the emulsion composition include a method of fractionating and fractionating by reverse phase liquid chromatography.

<Composition of emulsion composition>
The content of the liquid conjugated diene rubber in the emulsion composition of the present invention is an emulsion composition from the viewpoint of improving the stability of the emulsion and improving the adhesive strength when the emulsion composition is used as an adhesive. It is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 4% by mass or more, and preferably 50% by mass or less, based on the total amount of the substance. It is more preferably 30% by mass or less, and further preferably 20% by mass or less. When the content of the liquid conjugated diene rubber in the emulsion composition is within the above range, it is possible to improve the stability of the emulsion and prevent the viscosity of the emulsion composition from becoming extremely high.

The content of the diluent in the emulsion composition is preferably 1% by mass or more, more preferably 2% by mass or more, and 4% by mass or more, based on the total amount of the emulsion composition. Is more preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. When the content of the diluent in the emulsion composition is within the above range, it is possible to prevent the viscosity of the emulsion composition from becoming extremely high, and the production efficiency is improved. In addition, since the stability of the emulsion is improved, problems such as phase separation are less likely to occur for a long period of time after production.

The content of the surfactant in the emulsion composition is preferably 1 part by mass or more, preferably 3 parts by mass or more, based on 100 parts by mass of the total of the liquid conjugated diene rubber and the diluent. It is more preferable that the amount is 4 parts by mass or more. When the content of the surfactant is 1 part by mass or more, the stability of the emulsion can be improved. On the other hand, the amount of the surfactant is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of manufacturing cost.

The liquid conjugated diene rubber may be used alone or in combination of two or more. In addition, the diluent may be used alone or in combination of two or more. Further, the surfactant may be used alone or in combination of two or more.

Further, the emulsion composition of the present invention comprises a liquid conjugated diene rubber, a diluent having a vapor pressure of 10 Pa or less at 20 ° C., a surfactant, and other components other than water, as long as the stability of the emulsion is not impaired. May include.
Examples of the other components include other polymers, acids, basic compounds such as sodium hydroxide, antioxidants, curing agents, dispersants, pigments, dyes, adhesion aids, carbon black and the like.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and the like. Of these, sodium hydroxide and ammonia are preferable from the viewpoint of stability and adhesiveness, and ammonia is preferably used from the viewpoint of worker safety.

When the emulsion composition contains other components, the content thereof is preferably 1,000 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the liquid conjugated diene rubber. Yes, more preferably 10 parts by mass or less, still more preferably 1 part by mass or less. For example, when the emulsion composition contains a basic compound such as sodium hydroxide in the above range, the stability of the emulsion is further improved.

[Method for producing emulsion composition]
In the method for producing an emulsion composition of the present invention, the liquid conjugated diene rubber, the diluent, the surfactant, and water are mixed to produce an oil droplet emulsion in water, and then the diluent is not removed. It is characterized by.
According to the production method of the present invention, since a diluent having a vapor pressure of 10 Pa or less at 20 ° C. is used, stability is easily compared with the conventional method while suppressing an increase in the viscosity of the emulsion composition. It is possible to obtain an excellent emulsion composition.
Further, in the conventional method using a highly volatile solvent, a solvent removing step is required, but in the method of the present invention, it is possible to produce an emulsion composition without requiring the removing step. be. That is, according to the production method of the present invention, the emulsion composition can be efficiently used for an adhesive or the like without requiring a post-treatment step.
In the production method of the present invention, "not removing the diluent" means that it is not necessary to provide a step for removing the diluent.

The order in which the liquid conjugated diene rubber, the diluent, the surfactant and the water are mixed is as follows: the liquid conjugated diene rubber, the diluent and the surfactant are mixed, and then water is mixed therein. You may. A more preferred mixing order is to mix the liquid conjugated diene rubber and the diluent to prepare a diluent, then mix the diluent with the surfactant, then water and, if necessary, hydroxide. The order is to add basic compounds such as sodium little by little and mix them. The method for producing an emulsion composition adopting these orders is generally called a phase inversion emulsification method, in which an emulsifier is dissolved in an oil phase and water is added to the emulsion composition while stirring to change the continuous phase from the oil phase to the aqueous phase. This is a method of inverting the phase to form an O / W type emulsion. When water and, if necessary, a basic compound such as sodium hydroxide are mixed, the above-mentioned phase inversion can be slowly promoted by adding the mixture little by little, and the resulting emulsion composition can be obtained. Is finer and the particle size distribution is smaller. Further, when a basic compound such as sodium hydroxide is added, completing the addition of the basic compound before the above-mentioned phase inversion is completed improves the storage stability of the obtained emulsion composition. It is preferable in that it can be used.

When the liquid conjugated diene rubber, the diluent, and the surfactant are mixed, and then water is mixed with the liquid, each component is preferably mixed by a mechanical method. Examples of the mechanical method include a method using a kneader, a super mixer, and a twin-screw extruder, and these can be used alone or in combination. By using the above apparatus, an emulsion composition having a fine particle size can be obtained by applying strong shearing.

After preparing the diluted solution by mixing the liquid conjugated diene rubber and the diluent, the surfactant is mixed with the diluted solution, and then water and, if necessary, a basic compound such as sodium hydroxide are added. When the order of mixing while adding in small amounts is adopted, it is preferable to mix each step by the method shown below. That is, in the step of mixing the liquid conjugated diene rubber and the diluent to prepare a diluent, and the step of mixing the obtained diluent with the surfactant, a kneader, a super mixer, and a twin-screw extruder are used. It is preferable to mix using. By using these devices, it is possible to obtain a uniformly mixed liquid with high productivity relatively easily.
Then, in the step of mixing water and a basic compound such as sodium hydroxide little by little, a homogenizer, a homomixer, a disper mixer, a colloid mill, a kneader, a planetary mixer, a super mixer, a high-pressure homogenizer, and two A method of mixing using a shaft extruder, an ultrasonic emulsifier, or the like is mentioned as a preferable mixing method, and these can be used alone or in combination. By using the above apparatus, an emulsion composition having a fine particle size can be obtained by applying strong shearing.

When water is added in the method for producing an emulsion composition, the emulsion composition is once so that the contents of the liquid conjugated diene rubber and the diluent are within the above-mentioned suitable ranges. Water may be added in the manufacturing process of. In a more preferred embodiment, the manufacturing process of the emulsion composition is divided into two or more steps, and in the first manufacturing step, the amount of water added is limited so as to contain the liquid conjugated diene rubber and the diluent in a high concentration. Then, in the subsequent production process of the emulsion composition, a production process of further adding water so as to have the content of the liquid conjugated diene rubber and the diluent suitable for the final product is used. By adopting such a manufacturing process, the product quality of the finally obtained emulsion composition can be easily stabilized. Further, when this manufacturing process is adopted, it is not always necessary to perform the first manufacturing process and the second and subsequent manufacturing steps in the same place, and the high-concentration emulsion composition obtained in the first manufacturing step is used as the emulsion composition. After transporting to or near the place where it is actually used, water is added so as to have the content of the liquid conjugated diene rubber and the diluent suitable for the final product in the second and subsequent manufacturing processes of the emulsion composition. Embodiments such as further addition are also preferred. In this case, the high-concentration emulsion composition is preferable from the economical point of view because the transportation cost is relatively small.

According to the production method of the present invention, the viscosity of the diluted solution can be lowered, so that when emulsification is performed by the mechanical method, an excessive load is not applied to the apparatus and the rotation speed is increased to provide sufficient shear. Can be given. From the above viewpoint, the viscosity of the diluted solution measured at 25 ° C. is preferably 1.0 × 10 ³ Pa · s or less, and more preferably 5.0 × 10 ² Pa · s or less. It is more preferably 0.0 × 10 ² Pa · s or less, and most preferably 5.0 × 10 Pa · s or less. When the viscosity is within the above range, the viscosity can be sufficiently lowered, so that the production becomes easy.
The viscosity of the diluted solution means the viscosity measured at 25 ° C. using a Brookfield type viscometer (B type viscometer) having a composition in which only the conjugated diene rubber and the diluent are mixed. The rotor and rotation speed at the time of measurement are appropriately set so as to be close to full scale.

<Use of emulsion composition>
Since the emulsion composition of the present invention has high emulsion stability as described above, it exhibits excellent adhesiveness when used as an adhesive component of an adhesive, for example. When the emulsion composition of the present invention is used as an adhesive component, its use is not particularly limited, and examples thereof include applications for adhering fibers and rubber.

〔fiber〕
The fiber as an adherend is not particularly limited, but a hydrophilic fiber is preferable from the viewpoint of affinity with an adhesive using the emulsion composition. In the present invention, the term "fiber" includes not only single fibers and long fibers but also non-woven fabrics, woven fabrics, knitted fabrics, felts, sponges and the like.

The hydrophilic synthetic fiber is composed of a hydrophilic functional group such as a hydroxy group, a carboxy group, a sulfonic acid group, and an amino group, and / or a thermoplastic resin having a hydrophilic bond such as an amide bond. Synthetic fibers can be mentioned.
Specific examples of such a thermoplastic resin include polyvinyl alcohol-based resin and polyamide-based resin [polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 9C (polyamide composed of nonanediamine and cyclohexanedicarboxylic acid). And other aliphatic polyamides; semi-aromatic polyamides synthesized from aromatic dicarboxylic acids such as polyamide 9T (polyamide composed of nonanediamine and terephthalic acid) and aliphatic diamines; aromatic dicarboxylic acids and aromatics such as polyparaphenylene terephthalamide. Total aromatic polyamides synthesized from group diamines, etc.], polyacrylamide-based resins, etc. may be mentioned.
Among these, polyvinyl alcohol-based resins and polyamide-based resins are preferable. As the hydrophilic synthetic fiber, one kind may be used alone, or two or more kinds may be used in combination. Further, these hydrophilic synthetic fibers may be further subjected to a hydrophilization treatment described later in order to further increase the hydrophilicity.

Examples of the hydrophilic natural fiber include natural cellulose fibers such as wood pulp such as kraft pulp, cotton pulp, and non-wood pulp such as straw pulp.
Examples of the hydrophilic regenerated fiber include regenerated cellulose fibers such as rayon, lyocell, cupra, and polynosic.
Each of these natural fibers and regenerated fibers may be used alone or in combination of two or more. Further, these hydrophilic natural fibers and regenerated fibers may be further subjected to a hydrophilization treatment described later in order to further increase the hydrophilicity.

The hydrophilic fiber may have at least a hydrophilic surface. For example, a fiber having a hydrophilic treatment on the surface of the hydrophobic fiber or a core having a hydrophobic resin as a core and a sheath having a hydrophilic resin as a core. It may be a sheath type composite fiber or the like. For examples of hydrophilic resins constituting the sheath, the description of hydrophilic synthetic fibers is cited. Examples of the hydrophobic fiber made of a hydrophobic resin include polyolefin fibers such as polyethylene and polypropylene, polyester fibers such as polyethylene terephthalate, and all-aromatic polyester fibers, and among these, polyester fibers are preferable. ..

The hydrophilization treatment is not particularly limited as long as it is a treatment for chemically or physically imparting a hydrophilic functional group to the fiber surface, and for example, the hydrophobic fiber made of the hydrophobic resin is subjected to an isocyanate group, an epoxy group, or a hydroxy. It is carried out by a method of modifying with a compound containing a hydrophilic functional group such as a group, an amino group, an ether group, an aldehyde group, a carbonyl group, a carboxy group and a urethane group or a derivative thereof, or a method of modifying the surface by irradiation with an electron beam. be able to.

As the fiber used in the present invention, synthetic fiber and regenerated fiber are preferable from the viewpoint of easy compatibility between the emulsion composition and the fiber, and among them, polyvinyl alcohol fiber and regenerated cellulose fiber made from polyvinyl alcohol resin as a raw material. One or more selected from polyester fibers and polyamide fibers is preferable. Among them, the hydrophilized polyester fiber is the most preferable.

[Method of adhering emulsion composition to fibers]
The method for adhering the emulsion composition to the fiber is not particularly limited, and it is preferably performed by one or more selected from dipping, roll coater, oiling roller, oiling guide, nozzle (spray) coating, brush coating and the like.

The amount of the emulsion composition adhered is preferably 0.01 part by mass or more, and 0.1 part by mass or more with respect to 100 parts by mass of the fiber, from the viewpoint of improving the adhesiveness between the fiber and the rubber. It is more preferably 1 part by mass or more, and from the viewpoint of the balance between the production cost and the effect, it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. It is more preferably 3 parts by mass or less.

After the emulsion composition of the present invention is attached to the fiber, it is preferably allowed to acclimate at room temperature of about 20 ° C. for about 3 to 10 days. Further, in some cases, the fiber may be heat-treated after being attached to the fiber.
The heat treatment is preferably performed at a treatment temperature of 100 to 200 ° C. and a treatment time of 0.1 seconds to 2 minutes. Since the liquid conjugated diene rubber contained in the emulsion composition has a reactive multiple bond, the heat treatment in the presence of oxygen is preferably 200 ° C. or lower, more preferably 175 ° C. or lower. .. When the temperature of the heat treatment is within the above range, the adhesive strength can be improved without reducing the amount of reactive multiple bonds in the liquid conjugated diene rubber, the deterioration of the fibers can be suppressed, and coloring and the like can be suppressed. The quality is also good.

[Rubber]
The rubber that adheres to the fiber is not particularly limited, and for example, NR (natural rubber), IR (polyisoprene rubber), BR (polybutadiene rubber), SBR (styrene-butadiene rubber), NBR (nitrile rubber), EPM (ethylene-). Propylene copolymer rubber), EPDM (ethylene-propylene-non-conjugated diene copolymer rubber), IIR (butyl rubber), halogenated butyl rubber, CR (chloroprene rubber) and the like can be mentioned. Among these, it is more preferable to use NR, BR, and SBR. One type of these rubbers may be used alone, or two or more types may be used in combination.

As a method of adhering the fiber and the rubber to produce a rubber molded body, for example, an emulsion composition is adhered to the fiber, and the emulsion composition is embedded in the unvulcanized rubber component to obtain the rubber component. By vulcanizing the above, it is possible to obtain a molded product in which fibers and rubber are bonded via the emulsion composition.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to such Examples and the like.

<Manufacturing of liquid conjugated diene rubber>
Production Example 1: Production of Modified Conjugated Diene Rubber (A-1) A sufficiently dried 5 L autoclave is substituted with nitrogen, 1260 g of hexane and 36.3 g of n-butyllithium (17 mass% hexane solution) are charged, and the temperature is adjusted to 50 ° C. After raising the temperature, 1260 g of butadiene was sequentially added under stirring conditions while controlling the polymerization temperature to be 50 ° C., and the mixture was polymerized for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum dried at 70 ° C. for 24 hours to obtain unmodified liquid polybutadiene (A'-1).
Subsequently, 500 g of the obtained unmodified liquid polybutadiene (A'-1) was charged into a nitrogen-substituted autoclave having a capacity of 1 L, and 25 g of maleic anhydride and N-phenyl-N'-(1,3-dimethyl) were charged. 0.5 g of butyl) -p-phenylenediamine (trade name "Nocrack 6C", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) was added and reacted at 170 ° C. for 24 hours to obtain maleic anhydride-modified liquid polybutadiene. 8.5 g of methanol was added to 525 g of the obtained maleic anhydride-modified liquid polybutadiene and reacted at 80 ° C. for 6 hours to obtain monomethyl maleic acid-modified liquid polybutadiene (A-1).

Production Example 2: Production of Modified Conjugated Diene Rubber (A-2) 1260 g of hexane and 23.6 g of n-butyllithium (17 mass% hexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set under stirring conditions. A modified conjugated diene rubber (A-2) was produced in the same manner as in Production Example 1 except that 1260 g of butadiene was sequentially added while controlling the temperature to 50 ° C.

<Manufacturing of low-viscosity liquid rubber>
Production Example 3: Production of low-viscosity liquid butadiene rubber (B-1) A sufficiently dried 5 L autoclave is substituted with nitrogen, 1260 g of hexane and 166 g of n-butyllithium (17 mass% hexane solution) are charged, and the temperature is raised to 50 ° C. Then, under stirring conditions, 1260 g of butadiene was sequentially added while controlling the polymerization temperature to be 50 ° C., and the mixture was polymerized for 1 hour. Then, methanol was added to stop the polymerization reaction to obtain a polymer solution. Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. The polymer solution after washing was vacuum-dried at 70 ° C. for 24 hours to obtain a low-viscosity liquid butadiene rubber (B-1).

The measurement method and calculation method for each physical property of the modified conjugated diene-based rubber and the like are as follows. The results are shown in Table 1.
<Measurement method of weight average molecular weight, number average molecular weight and molecular weight distribution>
Mw, Mn and Mw / Mn of the modified conjugated diene rubber and the like were determined by GPC (gel permeation chromatography) as standard polystyrene conversion values. The measuring device and conditions are as follows.
-Device: GPC device "GPC8020" manufactured by Tosoh Corporation
-Separation column: "TSKgelG4000HXL" manufactured by Tosoh Corporation
-Detector: "RI-8020" manufactured by Tosoh Corporation
-Eluent: Tetrahydrofuran-Eluent flow rate: 1.0 ml / min-Sample concentration: 5 mg / 10 ml
-Column temperature: 40 ° C

<Measurement method of melt viscosity>
The melt viscosity of the modified conjugated diene rubber or the like at 38 ° C. was measured with a Brookfield type viscometer (manufactured by BROOKFIELD ENGINEERING LABS. INC.).

<Measurement method of glass transition temperature>
10 mg of the modified conjugated diene rubber was collected in an aluminum pan, and the thermogram was measured under the conditions of a heating rate of 10 ° C./min by differential scanning calorimetry (DSC), and the peak top value of DDSC was defined as the glass transition temperature.

<Average number of hydrogen-bonding functional groups per molecule>
The average number of hydrogen-bonding functional groups per molecule of modified conjugated diene-based rubber was calculated from the following formula from the equivalent of hydrogen-bonding functional groups (g / eq) of the modified conjugated diene-based rubber and the number average molecular weight Mn in terms of styrene. ..
Average number of hydrogen-bonding functional groups per molecule = [(number average molecular weight (Mn)) / (molecular weight of styrene unit) × (conjugated diene and, if necessary, average of other monomer units other than conjugated diene) Molecular weight)] / (equivalent to hydrogen-bonding functional group)
The method for calculating the equivalent of the hydrogen-bonding functional group can be appropriately selected depending on the type of the hydrogen-bonding functional group.

To calculate the average number of hydrogen-bonding functional groups per molecule of the modified conjugated diene-based rubber, the acid value of the modified conjugated diene-based rubber is obtained, and the equivalent of hydrogen-bonding functional groups (g / eq) is calculated from the acid value. I went by that.
The sample after the denaturation reaction was washed 4 times with methanol (5 mL per 1 g of the sample) to remove impurities such as antioxidants, and then the sample was dried under reduced pressure at 80 ° C. for 12 hours. 180 mL of toluene and 20 mL of ethanol were added to 3 g of the sample after the denaturation reaction to dissolve it, and then neutralized and titrated with an ethanol solution of 0.1N potassium hydroxide, and the acid value was determined from the following formula.
Acid value (mgKOH / g) = (AB) x F x 5.611 / S
A: Amount of 0.1N potassium hydroxide added to the ethanol solution required for neutralization (mL)
B: Amount (mL) of 0.1N potassium hydroxide in ethanol solution in a blank containing no sample.
F: Potency of 0.1N potassium hydroxide in ethanol solution S: Mass of weighed sample (g)

From the acid value, the mass of the hydrogen-bonding functional group contained in 1 g of the modified conjugated diene rubber is calculated by the following formula, and the mass other than the functional group contained in 1 g of the modified conjugated diene rubber (polymer main chain mass). ) Was calculated. Then, the equivalent of the hydrogen-bonding functional group (g / eq) was calculated from the following formula.
[Hydrogen-bonding functional group mass per gram] = [Acid value] / [56.11] × [Hydrogen-bonding functional group molecular weight] / 1000
[Polymer main chain mass per 1 g] = 1- [Hydrogen bond functional group mass per 1 g]
[Equivalent amount of hydrogen-bonding functional group] = [mass of polymer main chain per 1 g] / ([mass of hydrogen-bonding functional group per 1 g] / [molecular weight of hydrogen-bonding functional group])

The components used in Examples and Comparative Examples are as shown in Tables 2 and 3.

The vapor pressure of the diluent in Table 2 at 20 ° C. and the HLB value of the surfactant in Table 3 were measured according to the following method.
[Vapor pressure of diluent at 20 ° C]
The vapor pressures of synthetic oils and mineral oils at 20 ° C. are constants A, B, and C of Antoine equation: log10P = A- (B / (T + C)) based on the measured values measured by the gas flow method. Was calculated and then calculated.
The vapor pressure of toluene at 20 ° C. was directly measured by the static method.

[HLB value of surfactant]
To identify the nonionic surfactant, the molecular weight and structural units were detected and measured using mass spectra, the structure was detected and measured using 1H and ¹³ C ^- NMR, and the structure was identified based on these. Based on the identified information, the HLB value was obtained using the following formula (I) based on the Griffin method.
HLB = 20 × total formula weight of hydrophilic part / molecular weight (I)

<Example 1; Preparation of emulsion>
Modified conjugated diene rubber (A-1) as a liquid conjugated diene rubber and naphthenic oil (trade name "SUNTHENE 250J" manufactured by Nippon Sun Oil Co., Ltd.) as a diluent (oil) having a vapor pressure of 10 Pa or less at 20 ° C. , Vapor pressure at 20 ° C .: 1.0 × 10 ^-1 Pa) at the ratio shown in Table 4 and stirred for 24 hours while warmed to 50 ° C. for the modified conjugated diene rubber (A-1). 300 g of oil diene solution was prepared.
Next, 18 g of polyoxyethylene alkyl ether (trade name "TE-10A", manufactured by Toho Chemical Industry Co., Ltd., HLB value: 14.1) and 50% by mass sodium hydroxide aqueous solution were added to the oil dilute solution as a surfactant. .6 g was added and the mixture was stirred for 10 minutes. Subsequently, 210 g of water was added little by little with stirring, and the mixture was stirred for 60 minutes to obtain an emulsion composition (E-1) of the modified conjugated diene rubber (A-1).

<Examples 2 to 4, 7 to 8, Comparative Examples 1 to 3; Preparation of emulsion composition>
An emulsion composition was prepared by the same method as in Example 1 except that the composition of each component was as shown in Table 4.

<Examples 5 to 6; Preparation of emulsion composition>
It was carried out except that the composition of each component was as shown in Table 4 and that primary alcohol ethoxylate (trade name "TN-100", manufactured by ADEKA Corporation, HLB: 13.8) was used as a surfactant. An emulsion composition was prepared in the same manner as in Example 1.

[evaluation]
<Easy to manufacture (viscosity at the time of dilution)>
In Examples and Comparative Examples, the viscosity of the diluted solution immediately after mixing the liquid conjugated diene rubber and the diluent was measured with a rotary B-type viscometer (rotational speed 100 rpm). The measurement was performed at room temperature (25 ° C.). The lower the viscosity, the easier it is to manufacture.
In the present invention, "easy to manufacture" means that an emulsion composition having excellent stability can be easily manufactured. Specifically, when a liquid conjugated diene rubber and a diluent are mixed, the viscosity becomes high. It means that it is excellent in handleability and ease of manufacture without being excessively high.

<Stability of emulsion composition>
After preparing the emulsion compositions of Examples and Comparative Examples, they were placed in a sample bottle and allowed to stand at room temperature (25 ° C.) for 1 day. The emulsion composition in the sample bottle was visually observed, and the phase-separated volume of the total volume of the emulsion composition was evaluated according to the following criteria. The results are shown in Table 4.

〔standard〕
A: The phase-separated ratio is less than 10% of the total volume, and the stability is excellent.
B: The phase-separated ratio is 10% or more and less than 50% of the total volume, and the stability is somewhat poor.
C: The phase-separated ratio is 50% or more of the total volume, and the stability is poor.

<Adhesion to polyester fibers>
Regarding the adhesiveness to polyester fibers, reinforcing fibers were prepared according to the following procedure, and then an evaluation specimen was prepared. In the evaluation of the adhesiveness to the polyester fiber, the sum of the amounts of the liquid conjugated diene rubber, the diluent, the surfactant, and the sodium hydroxide in the formulation shown in Table 4 is 10% by mass of the whole (emulsion composition). Only for Examples 1, 3 and 5 and Comparative Examples 1 and 2, which are%. The results are shown in Table 4.
(1) Manufacture of reinforcing fibers [Constituent material of surface modification layer (surface modifier)]
First, the constituent material (C-1) of the surface modification layer was prepared by mixing the following components.
-Blocked isocyanate compound: 2.29 parts by mass-Epoxy compound: 0.8 parts by mass-Water: 96.91 parts by mass

The details of the compound used for C-1 are as follows.
-Blocked isocyanate compound Meicanate DM-3031 CONC (manufactured by Meisei Chemical Works, Ltd., pure content 54% by mass)
-Epoxy compound Denacol EX-614B (manufactured by Nagase Chemtech Co., Ltd., pure content 100% by mass)

[Handling method of twisted cord]
Next, the following twisted cord was treated with the constituent material (C-1) of the surface modification layer. Specifically, two PET fibers (total fineness 1100 dtex, single yarn fineness 6.10 dtex), which are polyester fibers, are twisted together by multiplying them by 470 times / m of upper twist and 470 times / m of lower twist. A fiber cord was made. Next, the twisted cord was immersed in the constituent material (C-1) of the surface modification layer, and then squeezed with a roller. The obtained fiber cord was dried at 140 ° C. for 60 seconds and further heat-treated at 240 ° C. for 60 seconds to prepare the fiber cord.

Next, the obtained fiber cord was immersed in an emulsion containing a modified conjugated diene rubber (A-1) or a modified conjugated diene rubber (A-2), squeezed with a roller, and dried at 140 ° C. for 60 seconds. Then, the reinforcing fiber was produced by winding it up.

(2) Preparation of Evaluated Specimen Three reinforcing fibers prepared were arranged at regular intervals on an NR / SBR unvulcanized rubber composition prepared by the formulation described below. Next, an evaluation specimen was prepared by press vulcanization at 150 ° C. and a pressure of 20 kg / cm ² for 30 minutes.

[Composite composition of NR / SBR unvulcanized rubber]
NR rubber: 70 parts by mass SBR rubber: 41.25 parts by mass Filler (carbon black): 45 parts by mass Vulcanizing agent (sulfur powder): 3.5 parts by mass Vulcanization aid (zinc flower, stealic acid): 6 parts by mass Vulcanization accelerator (thiazole type): 1 part by mass

(3) Evaluation Finally, the force (N / 3) required for T-shaped peeling of the obtained evaluation specimen from the rubber was measured, and the adhesiveness to the fiber was evaluated as the rubber adhesive force. The results are shown in Table 4.
The evaluation result of the rubber adhesive strength indicates that the larger the numerical value, the larger the adhesive strength between the reinforcing fiber and the rubber.
〔standard〕
A: When the adhesiveness to polyester fibers is 70N / 3 or more B: When the adhesiveness to polyester fibers is 40N / 3 or more and less than 70N / 3 C: The adhesiveness to polyester fibers is 40N When less than / 3 lines The numerical value in parentheses in the table is the measured value (N / 3 lines).

<Adhesion to polyamide fibers>
Regarding the adhesiveness to polyamide fibers, reinforcing fibers were prepared according to the following procedure, and then a test piece for evaluation was prepared.
In the evaluation of the adhesiveness to the polyamide fiber, the sum of the amounts of the liquid conjugated diene rubber, the diluent, the surfactant, and the sodium hydroxide in the formulation shown in Table 5 is 10% by mass of the whole (emulsion composition). Only for Example 7 which is%. The results are shown in Table 5.

(1) Manufacture of reinforcing fibers [Constituent material of surface modification layer (surface modifier)]
First, the constituent material (D-1) of the surface modification layer was prepared by mixing the following components.
-Polyethyleneimine compound: 0.01 parts by mass-Water: 99.99 parts by mass

The details of the compound used for D-1 are as follows.
-Polyethyleneimine compound (SP-200 manufactured by Nippon Shokubai Co., Ltd.)

[Handling method of twisted cord]
Next, the following twisted cord was treated with the constituent material (D-1) of the surface modification layer. Specifically, a twisted fiber cord is obtained by multiplying two nylon fibers (total fineness 1400 dtex, single yarn fineness 6.86 dtex), which are polyamide fibers, by 470 times / m of upper twist and 470 times / m of lower twist. Was produced. Next, the twisted cord was immersed in the constituent material (D-1) of the surface modification layer, and then squeezed with a roller. The obtained fiber cord was dried at 140 ° C. for 60 seconds and further heat-treated at 210 ° C. for 60 seconds to prepare the fiber cord.

Next, the obtained fiber cord was immersed in an emulsion containing a modified conjugated diene rubber (A-2), squeezed with a roller, dried at 140 ° C. for 60 seconds, and then wound to prepare a reinforcing fiber. ..

As is clear from the description of Examples and Comparative Examples, according to the present invention, an emulsion composition having excellent emulsion stability can be obtained. Further, it can be seen that when the emulsion composition of the present invention is used for adhesion, excellent adhesiveness is exhibited.

Claims (7)

1. An emulsion composition containing a liquid conjugated diene rubber, a diluent having a vapor pressure of 10 Pa or less at 20 ° C., a surfactant, and water.
2. The emulsion composition according to claim 1, wherein the liquid conjugated diene rubber contains a monomer unit derived from one or more selected from butadiene, isoprene, and β-farnesene.
3. The emulsion composition according to claim 1 or 2, wherein the liquid conjugated diene rubber is a modified conjugated diene rubber having a hydrogen-bonding functional group as a part of the conjugated diene rubber.
4. The hydrogen-binding functional group is a hydroxy group, an epoxy group, an aldehyde group, an acetalized form of an aldehyde group, a carboxy group, a salt of a carboxy group, an esterified form of a carboxy group, an acid anhydride of a carboxy group, a boronyl group, or a boronyl. The emulsion composition according to claim 3, wherein the emulsion composition is one or more selected from a group salt, an esterified body of a boronyl group, a silanol group, and an esterified product of a silanol group.
5. The emulsion composition according to any one of claims 1 to 4, wherein the surfactant is a nonionic surfactant.
6. Any of claims 1 to 5, wherein the content of the surfactant in the emulsion composition is 1 to 15 parts by mass with respect to 100 parts by mass in total of the liquid conjugated diene rubber and the diluent. The emulsion composition according to.
7. The method for producing an emulsion composition according to any one of claims 1 to 6, wherein the liquid conjugated diene rubber, the diluent, the surfactant, and water are mixed to produce an oil droplet emulsion in water. A method for producing an emulsion composition, which comprises not removing the diluent after the emulsion composition.